Using grazing incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy (AFM) it has been recently demonstrated that linear fluorocarbon-hydrocarbon diblocks (FnHm) self-assemble in water/air interfaces forming elongated and circular hemimicelles. Those structures have been observed for diblocks with at least eight fluorinated carbons. Based on the lack of a collapse pressure for F6H16, and due to the fact that no stable surface pressure values are reached under compression, it has been concluded that these molecules do not form stable monolayers. It has been also suggested that F6H16 and shorter diblocks desorb from the water surface under compression. It is not easy to accept that a significant concentration of so hydrophobic molecules can be stable in aqueous solution even when the employed experimental techniques were not able to clearly detect a well defined structure on the interface. In the present work the adsorption and arrangement of F6H16 and F6H10 at the water surface are studied by molecular dynamics (MD) simulations as a function of the available area per molecule. Starting from a random mixture, the spontaneous formation of elongated hemimicelles is observed for both systems when the area per molecule is higher than similar to 50 (A)over dot(2). For intermediate areas two pseudophases, one rich in hydrocarbons and the other with higher fluorocarbon concentration, are formed. For the systems with less than similar to 30 (A) over dot(2) available per molecule the formation of multilayers is observed. This is the first time that the dynamics and structure of perfluoroalkane (PFA) films, and in particular of hemimicelles on a liquid surface, are observed and characterized at atomic level. (C) 2008 Elsevier Inc. All rights reserved.